CN118281175A - Positive electrode lead plaster for long-life lead storage battery and preparation method thereof - Google Patents
Positive electrode lead plaster for long-life lead storage battery and preparation method thereof Download PDFInfo
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- CN118281175A CN118281175A CN202410362161.9A CN202410362161A CN118281175A CN 118281175 A CN118281175 A CN 118281175A CN 202410362161 A CN202410362161 A CN 202410362161A CN 118281175 A CN118281175 A CN 118281175A
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- lead
- sulfuric acid
- positive electrode
- mixed solution
- plaster
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- 239000011505 plaster Substances 0.000 title claims abstract description 63
- 238000003860 storage Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000011259 mixed solution Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 18
- 238000010008 shearing Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021485 fumed silica Inorganic materials 0.000 claims description 10
- 229960001922 sodium perborate Drugs 0.000 claims description 10
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 3
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 15
- 210000001787 dendrite Anatomy 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 238000005987 sulfurization reaction Methods 0.000 abstract description 4
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 abstract description 3
- 235000011151 potassium sulphates Nutrition 0.000 abstract description 3
- 229910001432 tin ion Inorganic materials 0.000 abstract description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 45
- 229910006529 α-PbO Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 229960003966 nicotinamide Drugs 0.000 description 2
- 235000005152 nicotinamide Nutrition 0.000 description 2
- 239000011570 nicotinamide Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011906 Death Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910006531 α-PbO2 Inorganic materials 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses positive electrode lead plaster for a long-life lead storage battery and a preparation method thereof, and belongs to the technical field of lead storage batteries. The additive adopts inorganic potassium stannate for the first time, and generates sulfuric acid to react to generate tin sulfate and potassium sulfate when meeting acid, and the effect of tin ions and potassium ions in the positive electrode has obvious effects of reducing the sulfuration of the polar plate and avoiding the short circuit of dendrite of the positive electrode. The invention also uses the combination of the Baton lead powder and the Shimadzu lead powder, the performance of the lead plaster assembled into the lead storage battery is obviously improved, the heavy current discharge is improved by 10%, and the cycle life is improved by 15%.
Description
Technical Field
The invention belongs to the technical field of lead storage batteries, and particularly relates to positive electrode lead plaster for a long-life lead storage battery and a preparation method thereof.
Background
The service life of a battery is a key performance index of the battery, and factors influencing the service life are very large, wherein a positive electrode active substance is particularly key.
The main components of the positive electrode active material are alpha-PbO 2 and beta-PbO 2, wherein alpha-PbO 2 is used as a framework structure and is also used as a conductor, and plays a role in collecting current in the charge and discharge process, and beta-PbO 2 is used as an energy structure and is attached to the framework structure to participate in main charge and discharge to provide energy output and storage. Analysis of the end-of-life battery shows that the content of beta-PbO 2 is very high, and the alpha-PbO 2 is obviously reduced compared with the initial state, and it is inferred that a certain amount of alpha-PbO 2 is converted into beta-PbO 2,α-PbO2 to be continuously disintegrated and converted in the charge and discharge processes in the cycle process, so that collapse of an active substance skeleton can be caused, the current collecting effect of the battery is reduced, the internal resistance is increased, the utilization rate of active substances is reduced, and the capacity of the battery is reduced.
The invention discloses a long-service-life lead storage battery with publication number CN109273716B and a preparation method thereof. The preparation method of the lead storage battery comprises the following steps: the lead plaster of the positive plate is divided into two parts, namely, a first lead plaster containing stannous sulfate, antimonous oxide and 3BS and a second lead plaster containing 4BS are respectively prepared, then a sandwich plaster coating operation is carried out, the first lead plaster is coated on the inner layer, and then the second lead plaster is coated on the surface layer, so that a green plate is obtained; and (3) preparing a positive plate after medium-temperature curing, and then internally forming after assembling the battery, wherein the internal forming is initially charged by adopting a larger current density, so that the long-life lead storage battery is prepared. The invention adopts the sandwich paste, so that the surface layer of the green polar plate has high content of 4BS, the sulfation speed of the surface layer is relieved, and the content of alpha-PbO 2 of the surface layer is improved by combining a heavy current formation process, the softening speed of the surface layer of the polar plate is reduced in the process of battery circulation, and the cycle life of the battery is prolonged.
The patent document (CN 109273712A) discloses a lead storage battery positive electrode lead plaster and a preparation method thereof, and belongs to the technical field of storage batteries, wherein the positive electrode lead plaster comprises, by weight, 100 parts of lead powder, 3-7 parts of lead dioxide, 0.001-0.1 part of (iso) niacinamide, 0.01-0.5 part of polyester fiber, 0.02-0.5 part of antimony trioxide, 0.02-0.5 part of stannous sulfate and 0.02-0.2 part of carbon material. The invention utilizes the good conductivity of the alpha-PbO 2 to play the role of the conductive framework structure in the battery formation to improve the formation efficiency and shorten the formation time; in addition, the alpha-PbO 2 has good electrochemical stability, a good framework structure is kept in the use of the battery, and meanwhile, (iso) niacinamide can be effectively adsorbed on the surfaces of PbO 2 and a lead sulfate crystal structure to improve the performance of the polar plate, so that the cycle life of the battery is prolonged.
It can be seen that the modification of the positive electrode lead plaster by the additive is an effective method for improving the performance of the lead storage battery.
Disclosure of Invention
The invention provides a positive electrode lead plaster for a long-life lead storage battery and a preparation method thereof, and aims to solve the problems of sulfuration phenomenon and dendrite short circuit existing in a positive plate of the lead storage battery and improve the cycle life of the lead storage battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The invention provides a positive electrode lead plaster for a long-life lead storage battery, which comprises the following components in parts by weight: 100 parts of lead powder, 0.2-0.5 part of potassium stannate, 0.5-0.6 part of tetrabasic lead sulfate, 0.08-0.1 part of sodium perborate, 0.2-0.3 part of crystalline flake graphite, 0.5-1 part of fumed silica, 0.3-0.4 part of sodium carboxymethylcellulose and 0.1-0.15 part of polyester staple fibers.
The additive adopts inorganic potassium stannate for the first time, has white crystal powder in appearance, is easy to dissolve in water, is alkaline, generates sulfuric acid reaction when meeting acid to generate tin sulfate and potassium sulfate, has the effect of tin ions and potassium ions in the positive electrode, and has obvious effects of reducing the sulfuration of the polar plate and avoiding the short circuit of dendrites of the positive electrode.
The positive electrode lead plaster for the long-life lead storage battery also comprises 11-12 parts of water and 7-10 parts of sulfuric acid, wherein the density of the sulfuric acid is 1.4g/cm 3.
Preferably, the lead powder comprises Baton type lead powder and Shimadzu lead powder, wherein the Baton type lead powder is 25-35 parts, and the Shimadzu lead powder is 65-75 parts. The oxidation number of the Barton type lead powder is 83% -90%.
The lead powder produced by the Baton lead powder machine adopted by the invention adopts refined lead, wherein Pb is more than or equal to 99.95 percent, bi is less than or equal to 0.02 percent, sb is less than or equal to 0.02 percent, and the other lead powder meets the national standard GB/T469-20051 # lead ingot (copper Cu is less than or equal to 0.0005; arsenic As is less than or equal to 0.0005; zinc Zn is less than or equal to 0.0005; iron Fe is less than or equal to 0.0005). The invention adopts one third of Baton lead powder, which is equal to three times of the total bismuth and antimony in the lead powder, and finally the bismuth Bi in the lead powder is less than or equal to 0.0067 percent, the antimony is less than or equal to 0.0067 percent, and the content standard requirements of refined lead bismuth in normal production are met, wherein the bismuth Bi is less than or equal to 0.007 percent, and the antimony is less than or equal to 0.007 percent.
20% -30% Of the Baton type lead powder is alpha-PbO, the rest is beta-PbO, 100% of the Shimadzu type lead powder is beta-PbO, after the battery is charged, alpha-PbO in the anode is converted into alpha-PbO 2, beta-PbO is converted into beta-PbO 2, the dendrite chain length of alpha-PbO 2 is much larger than that of beta-PbO 2 in microcosmic, the positive plate produced by adding the lead powder produced by the Baton type lead powder machine has more long crystal chain structures than that of the positive plate produced by only adopting the Shimadzu type lead powder machine, the crystal chain structures play a role of a framework in the positive plate, active substances can be prevented from softening and falling off, the dendrite chain can be gradually shortened in the use process of the battery, finally disappears, the active substances of the positive plate are softened and fall off, and the long dendrite chain has better crystal chain retention life than the short dendrite chain.
Although only about one third of the lead powder adopted by the invention is the Barton lead powder, the lead powder still has good service life compared with a battery produced by only using the Shimadzu lead powder.
The invention also provides a preparation method of the positive electrode lead plaster for the long-life lead storage battery, which comprises the following steps:
(1) Firstly, mixing potassium stannate and sodium perborate, adding a first dose of water, and heating and dissolving to obtain a mixed solution A;
(2) Adding fumed silica and sodium carboxymethyl cellulose into a second dose of sulfuric acid solution, and heating and shearing to obtain a mixed solution B;
(3) Dry-mixing other component raw materials, spraying the mixed solution A, spraying the rest water, and uniformly mixing to obtain a mixture;
(4) And (3) pouring the rest sulfuric acid solution into the mixture in the step (3) under the negative pressure state, uniformly mixing, pouring the mixed solution B, uniformly mixing, and discharging the paste.
Preferably, in the step (1) and the step (2), the heating temperature is 60-70 ℃;
In the step (2), the shearing speed is 2500-3500 rpm, and the shearing time is 30-50 min. Is convenient for dissolving the raw materials.
In the step (1) and the step (3), the mass ratio of the first dosage of water to the rest water is 1:10-11;
In the step (1) and the step (4), the mass ratio of the first dose of sulfuric acid solution to the rest sulfuric acid solution is 3:4-7.
Further, in the step (3), the time of spraying the mixed solution A is 2-3 min, and the time of spraying the residual water is 4-6 min; in the step (4), the time for pouring the rest sulfuric acid solution is 3-5 min, and the time for pouring the mixed solution B is 3-5 min.
Preferably, in the step (4), the negative pressure state is-0.02 to-0.04 Mpa, the boiling point of water is reduced under the negative pressure, the volatilization amount of water at low temperature is improved, and the volatilized water takes away heat, so that the cooling speed is improved.
The temperature is controlled to be not higher than 85 ℃ when the rest sulfuric acid solution and the mixed solution B are poured in, the negative pressure value can be increased when the temperature is too high, and the temperature is reduced more rapidly when the negative pressure is larger; the temperature control can avoid the phenomenon of thermal runaway in the paste machine, the temperature control is carried out by utilizing the cooling system control of the paste machine, the growth of 3BS and lead sulfate crystals is kept, and the formation of 4BS crystals with larger size (the 4BS lead paste polar plate is difficult to be formed) is avoided.
The density of the lead plaster is low, and the lead plaster is stirred by opening an atmospheric exhaust system; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3. The control of the paste-making temperature can avoid the change of the apparent specific gravity of the lead paste caused by the water carried away by heat dissipation of the lead paste after paste-making, and simultaneously, the lead paste is prevented from influencing the paste-making quality (the bonding tightness degree of the lead paste and a grid) when contacting with a cold grid due to the higher temperature during the plate coating process, and further influencing the formation of a grid lead paste interface corrosion layer during the curing process.
The invention also provides a lead storage battery, which comprises a positive plate, a negative plate, a separator and electrolyte, wherein the positive plate is prepared from the positive lead plaster for the long-service-life lead storage battery.
The invention has the beneficial effects that:
The additive adopts inorganic potassium stannate for the first time, and generates sulfuric acid to react to generate tin sulfate and potassium sulfate when meeting acid, and the effect of tin ions and potassium ions in the positive electrode has obvious effects of reducing the sulfuration of the polar plate and avoiding the short circuit of dendrite of the positive electrode. The invention also uses the combination of the Baton lead powder and the Shimadzu lead powder, the performance of the lead plaster assembled into the lead storage battery is obviously improved, the heavy current discharge is improved by 10%, and the cycle life is improved by 15%.
Detailed Description
The manufacturing process of the invention is as follows:
1. and (3) preparing a mixed solution:
(1) Mixing 0.2-0.5 part of potassium stannate and 0.05-0.15 part of sodium perborate, adding into 1 part of water, heating to 60-70 ℃, mixing, stirring and dissolving for 10 minutes for later use to prepare a mixed solution A;
(2) Adding 0.5-1 part of fumed silica and 0.2-0.5 part of sodium carboxymethyl cellulose into an ultrasonic shearing machine, adding 3 parts of dilute sulfuric acid solution, heating to 60-70 ℃, shearing and stirring at the speed of 2500-3500 r/min for 30-50 minutes, and standing at the temperature of normal temperature to obtain a mixed solution B.
2. Lead plaster manufacturing process
(1) Putting 25-35 parts of Baton lead powder, 65-75 parts of Shimadzu lead powder, 0.2-0.3 part of crystalline flake graphite, 0.5-0.6 part of tetrabasic lead sulfate and 0.1-0.15 part of polyester staple fiber into a lead powder machine, and carrying out dry stirring and mixing;
(2) Then, the mixed solution A is sprayed for 2 to 3 minutes, then the rest formula water (formula water quantity minus 1 part) is sprayed for 4 to 6 minutes, and stirring is continued for 3 to 5 minutes;
(3) Opening a vacuum negative pressure system, adjusting the negative pressure to be minus 0.02 to minus 0.04Mpa, then pouring the rest of formula acid (the formula acid amount is subtracted by 3 parts), pouring for 3 to 5 minutes, stirring for 1 to 2 minutes, then pouring the mixed liquid B, pouring for 3 to 5 minutes, stirring for 5 to 10 minutes, controlling the highest temperature to be not higher than 85 ℃, controlling the temperature to be higher, increasing the negative pressure value, and enabling the negative pressure to be higher and the temperature to be lower.
(4) Stopping the machine for testing, wherein the density of the lead plaster is low, and the normal pressure exhaust system is opened for stirring; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3.
The following detailed description refers to the specific examples.
Example 1
1. And (3) preparing a mixed solution:
(1) Mixing 0.5 part of potassium stannate and 0.1 part of sodium perborate, adding 1 part of water, heating to 65 ℃, mixing, stirring and dissolving for 10 minutes for later use to prepare a mixed solution A;
(2) 0.6 part of fumed silica and 0.3 part of sodium carboxymethylcellulose are added into an ultrasonic shearing machine, 3 parts of dilute sulfuric acid solution is added, the temperature is heated to 65 ℃, shearing and stirring are carried out at a speed of 3000r/min for 40 minutes, and the standing temperature is kept at normal temperature, so that a mixed solution B is prepared.
2. Lead plaster manufacturing process
(1) Putting 35 parts of Baton lead powder, 65 parts of Shimadzu lead powder, 0.25 part of crystalline flake graphite, 0.6 part of tetrabasic lead sulfate and 0.1 part of polyester staple fiber into a lead powder machine, and carrying out dry stirring and mixing;
(2) Then, the mixed solution A is poured in for 3 minutes, then the rest formula water (formula water quantity minus 1 part) is poured in for 5 minutes, and stirring is continued for 5 minutes;
(3) Opening a vacuum negative pressure system, adjusting the negative pressure to be-0.03 Mpa, then pouring the rest of formula acid (formula acid amount minus 3 parts), pouring for 5 minutes, stirring for 2 minutes, then pouring the mixed liquid B, pouring for 5 minutes, stirring for 8 minutes, controlling the highest temperature to be not higher than 85 ℃, and controlling the negative pressure value to be raised when the temperature is too high, wherein the negative pressure is larger and the temperature is reduced more quickly.
(4) Stopping the machine for testing, wherein the density of the lead plaster is low, and the normal pressure exhaust system is opened for stirring; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3.
Example 2
1. And (3) preparing a mixed solution:
(1) Mixing 0.2 part of potassium stannate and 0.08 part of sodium perborate, adding into 1 part of water, heating to 70 ℃, mixing, stirring and dissolving for 10 minutes for later use to prepare a mixed solution A;
(2) 1 part of fumed silica and 0.3 part of sodium carboxymethylcellulose are added into an ultrasonic shearing machine, 3 parts of dilute sulfuric acid solution is added, the mixture is heated to 70 ℃, sheared and stirred for 50 minutes at 3500r/min, and the mixture is kept stand until the temperature reaches normal temperature, so that a mixed solution B is prepared.
2. Lead plaster manufacturing process
(1) Putting 25 parts of Baton lead powder, 75 parts of Shimadzu lead powder, 0.2 part of crystalline flake graphite, 0.8 part of tetrabasic lead sulfate and 0.1 part of polyester staple fiber into a lead powder machine, and carrying out dry stirring and mixing;
(2) Then, the mixed solution A is poured in for 3 minutes, then the rest formula water (formula water quantity minus 1 part) is poured in for 6 minutes, and stirring is continued for 5 minutes;
(3) Opening a vacuum negative pressure system, adjusting the negative pressure to be minus 0.04Mpa, then pouring the rest of formula acid (formula acid amount minus 3 parts), pouring for 5 minutes, stirring for 2 minutes, then pouring the mixed liquid B, pouring for 5 minutes, stirring for 8 minutes, controlling the highest temperature to be not higher than 85 ℃, and controlling the negative pressure value to be higher when the temperature is too high, wherein the negative pressure is higher and the temperature is reduced faster.
(4) Stopping the machine for testing, wherein the density of the lead plaster is low, and the normal pressure exhaust system is opened for stirring; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3.
Example 3
1. And (3) preparing a mixed solution:
(1) Mixing 0.4 part of potassium stannate and 0.1 part of sodium perborate, adding into 1 part of water, heating to 60 ℃, mixing, stirring and dissolving for 10 minutes for later use to prepare a mixed solution A;
(2) 0.5 part of fumed silica and 0.4 part of sodium carboxymethylcellulose are added into an ultrasonic shearing machine, 3 parts of dilute sulfuric acid solution is added, the mixture is heated to 60 ℃, sheared and stirred at the speed of 2500r/min for 40 minutes, and the mixture is kept stand until the temperature reaches normal temperature, so that a mixed solution B is prepared.
2. Lead plaster manufacturing process
(1) Putting 30 parts of Baton lead powder, 70 parts of Shimadzu lead powder, 0.3 part of crystalline flake graphite, 0.5 part of tetrabasic lead sulfate and 0.15 part of polyester staple fiber into a lead powder machine, and carrying out dry stirring and mixing;
(2) Then, the mixed solution A is poured in for 3 minutes, then the rest formula water (formula water quantity minus 1 part) is poured in for 5 minutes, and stirring is continued for 5 minutes;
(3) Opening a vacuum negative pressure system, adjusting the negative pressure to be-0.03 Mpa, then pouring the rest of formula acid (formula acid amount minus 3 parts), pouring for 3 minutes, stirring for 2 minutes, then pouring the mixed liquid B, pouring for 3 minutes, stirring for 8 minutes, controlling the highest temperature to be not higher than 85 ℃, and controlling the negative pressure value to be increased when the temperature is too high, wherein the negative pressure is larger and the temperature is reduced more rapidly.
(4) Stopping the machine for testing, wherein the density of the lead plaster is low, and the normal pressure exhaust system is opened for stirring; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3.
Comparative example 1 (without potassium stannate, without barton lead powder)
1. And (3) preparing a mixed solution:
(1) Mixing 0.1 part of sodium perborate, adding into 1 part of water, heating to 65 ℃, mixing, stirring and dissolving for 10 minutes for later use to prepare a mixed solution A;
(2) 0.8 part of fumed silica and 0.4 part of sodium carboxymethylcellulose are added into an ultrasonic shearing machine, 3 parts of dilute sulfuric acid solution is added, the mixture is heated to 65 ℃, sheared and stirred at a speed of 3000r/min for 40 minutes, and the mixture is kept stand until the temperature reaches normal temperature, so that a mixed solution B is prepared.
2. Lead plaster manufacturing process
(1) Putting 100 parts of Shimadzu lead powder, 0.25 part of crystalline flake graphite, 0.8 part of tetrabasic lead sulfate and 0.1 part of polyester staple fiber into a lead powder machine, and carrying out dry stirring and mixing;
(2) Then, the mixed solution A is poured in for 3 minutes, then the rest formula water (formula water quantity minus 1 part) is poured in for 5 minutes, and stirring is continued for 4 minutes;
(3) Opening a vacuum negative pressure system, adjusting the negative pressure to be-0.03 Mpa, then pouring the rest of formula acid (formula acid amount minus 3 parts), pouring for 4 minutes, stirring for 2 minutes, then pouring the mixed liquid B, pouring for 5 minutes, stirring for 10 minutes, controlling the highest temperature to be not higher than 85 ℃, and controlling the negative pressure value to be increased when the temperature is too high, wherein the negative pressure is larger and the temperature is reduced more rapidly.
(4) Stopping the machine for testing, wherein the density of the lead plaster is low, and the normal pressure exhaust system is opened for stirring; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3.
Comparative example 2 (without Potassium stannate, with Baton lead powder)
1. And (3) preparing a mixed solution:
(1) Mixing 0.1 part of sodium perborate, adding into 1 part of water, mixing and stirring at 65 ℃ for 10 minutes for later use to prepare a mixed solution A;
(2) 0.8 part of fumed silica and 0.4 part of sodium carboxymethylcellulose are added into an ultrasonic shearing machine, 3 parts of dilute sulfuric acid solution is added, the mixture is heated to 65 ℃, sheared and stirred at a speed of 3000r/min for 50 minutes, and the mixture is kept stand until the temperature reaches normal temperature, so that a mixed solution B is prepared.
2. Lead plaster manufacturing process
(1) Putting 30 parts of Baton lead powder, 70 parts of Shimadzu lead powder, 0.25 part of crystalline flake graphite, 0.7 part of tetrabasic lead sulfate and 0.1 part of polyester staple fiber into a lead powder machine, and carrying out dry stirring and mixing;
(2) Then, the mixed solution A is poured in for 3 minutes, then the rest formula water (formula water quantity minus 1 part) is poured in for 5 minutes, and stirring is continued for 5 minutes;
(3) Opening a vacuum negative pressure system, adjusting the negative pressure to be-0.03 Mpa, then pouring the rest of formula acid (formula acid amount minus 3 parts), pouring for 5 minutes, stirring for 2 minutes, then pouring the mixed liquid B, pouring for 5 minutes, stirring for 10 minutes, controlling the highest temperature to be not higher than 85 ℃, and controlling the negative pressure value to be increased when the temperature is too high, wherein the negative pressure is larger and the temperature is reduced more rapidly.
(4) Stopping the machine for testing, wherein the density of the lead plaster is low, and the normal pressure exhaust system is opened for stirring; adding pure water slightly with high density, mixing and stirring for 2-3 minutes until the density reaches the requirement, and using the lead plaster when the temperature of the lead plaster is less than or equal to 45 ℃ and the density of the lead plaster is 4.2-4.3 g/cm 3.
Test example 1
Positive electrode lead pastes prepared in examples 1 to 3 and comparative examples 1 to 2 were produced into plates, which were then equipped into 6-DZF-20 secondary batteries.
1. 2H rate discharge: according to 5.5 of the national battery standards GB/T22199-2017, after the storage battery is fully charged, the storage battery is kept still for 1-24 hours in an environment with the temperature of 25+/-2 ℃, and when the current constant current of 10A is used for discharging the battery voltage to be 10.5V, the capacity Ca with the rate of 2 hours reaches the C2 standard in three cycles.
2. High-current discharge: according to 5.5 of the national battery standards GB/T22199-2017, after the storage battery is fully charged, standing for 1-4 hours in an environment with the temperature of 25+/-5 ℃, and stopping discharging when the current of 3.6A reaches the voltage of 10.5V of the storage battery, wherein the discharge duration is not less than 25 minutes.
3. Cycle life: according to 5.12 of battery national standard GB/T22199-2017, discharging for 1.6h at 10A current in an environment with the temperature of 25+/-5 ℃, then charging for 6.4h at constant voltage of 16V (current limiting 4A) as one cycle time, and when the terminal voltage of the battery is discharged for 1.6h for three times and is lower than 10.5V continuously, ending the cycle life of the battery, and the total cycle life is not lower than 350 times.
4. The results of the detection are shown in Table 1 below.
TABLE 1
| Test sample | Capacity at room temperature/min | High current discharge/min | Cycle number/times |
| Comparative example 1 | 128.2 | 28 | 365 |
| Comparative example 2 | 128.8 | 28 | 378 |
| Example 1 | 129.1 | 30 | 410 |
| Example 2 | 128.8 | 31 | 417 |
| Example 3 | 128.2 | 31 | 427 |
As can be seen from the results in Table 1, the additive and lead plaster prefabrication technology of the invention has the advantages of substantially uniform capacity, about 10% improvement in heavy current discharge, about 15% improvement in service life, and remarkable effect.
Claims (10)
1. The positive electrode lead plaster for the long-life lead storage battery is characterized by comprising the following components in parts by weight: 100 parts of lead powder, 0.2-0.5 part of potassium stannate, 0.5-0.6 part of tetrabasic lead sulfate, 0.08-0.1 part of sodium perborate, 0.2-0.3 part of crystalline flake graphite, 0.5-1 part of fumed silica, 0.3-0.4 part of carboxyl metal cellulose and 0.1-O.15 part of polyester staple fiber.
2. The positive electrode lead plaster for long-life lead storage batteries according to claim 1, wherein the components further comprise water and sulfuric acid, wherein the pure water is 11-12 parts, the dilute sulfuric acid is 7-10 parts, and the density of the dilute sulfuric acid is 1.4g/cm 3.
3. The positive electrode lead plaster for long-life lead storage batteries according to claim 1, wherein the lead powder comprises barton type lead powder and shimadzu type lead powder, wherein the barton type lead powder is 25-35 parts and the shimadzu type lead powder is 65-75 parts.
4. The positive electrode lead plaster for long-life lead storage batteries according to claim 3, wherein said oxidation number of said barton lead powder is 83 to 90%.
5. The method for preparing the positive electrode lead plaster for the long-life lead storage battery according to any one of claims 1 to 4, which is characterized by comprising the following steps:
(1) Firstly, mixing potassium stannate and sodium perborate, adding a first dose of water, and heating and dissolving to obtain a mixed solution A;
(2) Adding fumed silica and sodium carboxymethyl cellulose into a second dose of sulfuric acid solution, and heating and shearing to obtain a mixed solution B;
(3) Dry-mixing other component raw materials, spraying the mixed solution A, spraying the rest water, and uniformly mixing to obtain a mixture;
(4) And (3) pouring the rest sulfuric acid solution into the mixture in the step (3) under the negative pressure state, uniformly mixing, pouring the mixed solution B, uniformly mixing, and discharging the paste.
6. The method according to claim 5, wherein in the steps (1) and (2), the heating temperature is 60 to 70 ℃;
In the step (2), the shearing speed is 2500-3500 rpm, and the shearing time is 30-50 min.
7. The method according to claim 5, wherein in the step (1) and the step (3), the mass ratio of the first dose amount of water to the remaining amount of water is 1:10-11;
In the step (1) and the step (4), the mass ratio of the first dose of sulfuric acid solution to the rest sulfuric acid solution is 3:4-7.
8. The preparation method according to claim 5, wherein in the step (3), the mixed solution A is sprayed for 2-3 min, and the residual water is sprayed for 4-6 min;
In the step (4), the time for pouring the rest sulfuric acid solution is 3-5 min, and the time for pouring the mixed solution B is 3-5 min.
9. The method according to claim 5, wherein in the step (4), the negative pressure is-0.02 to-0.04 MPa,
The control temperature is not higher than 85 ℃ when the rest sulfuric acid solution and the mixed solution B are poured in,
The temperature of the paste is not higher than 45 ℃,
The density of the lead plaster is 4.2-4.3 g/cm 3.
10. A lead storage battery comprising a positive plate, a negative plate, a separator and an electrolyte, wherein the positive plate is prepared by using the positive lead plaster for the long-life lead storage battery according to any one of claims 1 to 4.
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